Synthesis and Characterization of Nano TiO2 with

Sol-Gel Method as Self-Cleaning Agent on Acrylic

Paint
*Note: Sub-titles are not captured in Xplore and should not be used

XXX-X-XXXX-XXXX-X/XX/$XX.00 ©20XX IEEE

 line 1: 1st Given Name Surname
line 1: 2nd Given Name Surname line 1: 3rd Given Name Surname
line 2: dept. name of organization
line 2: dept. name of organization line 2: dept. name of organization
(of Affiliation)
(of Affiliation) (of Affiliation)
line 3: name of organization
line 3: name of organization line 3: name of organization
(of Affiliation)
(of Affiliation) (of Affiliation)
line 4: City, Country
line 4: City, Country line 4: City, Country
line 5: email address
line 5: email address line 5: email address
line 1: 4th Given Name Surname
line 1: 5th Given Name Surname line 1: 6th Given Name Surname
line 2: dept. name of organization
line 2: dept. name of organization line 2: dept. name of organization
(of Affiliation)
(of Affiliation) (of Affiliation)
line 3: name of organization
line 3: name of organization line 3: name of organization
(of Affiliation)
(of Affiliation) (of Affiliation)
line 4: City, Country
line 4: City, Country line 4: City, Country
line 5: email address
line 5: email address line 5: email address
 Abstract— Metal oxide TiO 2 has photocatalytic properties
that make TiO2 amphilic, that is, hydrophobic in the dark
(without UV light) and hydrophilic in the light (there is UV
light). The photocatalytic properties of TiO 2 can be utilized to
develop self-cleaning materials in paints. Self-cleaning material
is a material capable of cleaning itself both by avoiding it and
by degrading the dirt that clings to it with the help of UV rays.
The TiO2 nano particle synthesis process uses the sol-gel
method with the precursor tetrabuthyl titanate (TBT). The
purpose of this research is to synthesize TiO 2 nano particles as
self-cleaning material in paint with the most appropriate
composition. The results obtained from the synthesis of nano
TiO2 particles were tested by FTIR and appeared at a peak of
467.50 cm-1 indicating the presence of TiO 2 groups. In addition,
characterization using XRD was also produced which
produced the anatase crystalline phase of TiO 2 with a crystal
size of 24.32 nm. Surface morphology was analyzed by
Scanning Electron Microscopy (SEM). The ability of self-
cleaning properties in paint was measured through
hydrophobic properties through contact angle measurements
and the best contact angle values obtained on TiO 2 / paint (2: 8)
were 102.2o.
Keywords— nano TiO2, sol-gel, self-cleaning, hidrofobic
I. INTRODUCTION
Currently the development of nanoparticle technology
has been widely used in various purposes, one of which is as
a developer of self-cleaning properties. Self-cleaning
properties are properties where a material is able to clean
itself both by avoiding it and by degrading the dirt that
adheres to itself. One of these self-cleaning properties can be
applied to wall paints. Wall paint used by the community is
often difficult to clean from dirt or ink so self-cleaning
properties need to be developed in the paint to simplify the
maintenance process.
Development of the properties of paint is needed to
overcome the above problems. The paint is expected to
degrade the dirt or stains on the wall itself. This property is
called "self-cleaning". Self-cleaning properties on the surface
of the fabric work with the photocatalytic principle that
works when the surface gets ultraviolet (UV) radiation. The
photocatalysis process makes TiO2 hydrophilic, which is
very like water when exposed to UV rays, the impact of
nano-sized TiO2 surface remains transparent and not foggy
when exposed to water vapor, while in the dark (no UV rays)
TiO2 is hydrophobic or does not like water. In a world of
light and dark cycles, TiO2 behaves amphilic, hydrophobic
when dark and hydrophilic when bright [1].
The mechanism of the amphilic properties of TiO2 occurs
due to the presence of UV light. The presence of UV light on
TiO2 results in the transition of electrons (e-) from the
valence band to the conduction band, thus producing a
vacancy (h+) on the valence band and electrons (e-) on the
conduction band. Electrons reduce Ti (IV) to Ti (III), while a
vacuum (h+) oxidizes O2- to O2 resulting in an oxygen
vacuum on the surface. The oxygen vacuum is filled with
water molecules that bind with Ti (III) which then
decomposes into hydroxo on the surface. Furthermore, the
hydroxso undergoes condensation by releasing water to form
a hydrophobic Ti-O-Ti bond [2].
The development of TiO2 nano particle synthesis method
is needed to control the crystalline phase, size, and
morphology of TiO2 nanocrystals. Synthesis of TiO2
nanoparticles can be done by the sol-gel method. The sol-gel
method is a method of synthesis of nanoparticles where in
the process a phase change occurs from a colloidal
suspension (sol) forming a continuous liquid phase (gel). The
advantages of the sol-gel method for the synthesis of metal
oxide nanoparticles include forming a transparent oxide layer
that adheres perfectly to the fabric, resulting in uniform
particle size distribution and a large surface area [3].
Based on this information, a self-cleaning material from
TiO2 surface paint will be made in this study. Mixing paint
with TiO2 will be carried out with several different volume
compositions, namely the mass (gr) ratio of TiO 2 / paint
mixture of 0.5: 9.5; 1: 9; 1.5: 8.5; and 2:8. In this research
the characterization of TiO2 nanoparticles will be tested using
X-Ray Diffraction (XRD) and Fourier Transfrom Infra Red
(FTIR) instruments. The self-cleaning test will be measured
by the strength of the hydrophobic activity obtained by
measuring the angle of contact of water with the paint / TiO 2
coated glass surface.
II. METHODS
A. Tool
The tools used in this study are glass, dropper pipette,
beaker, measuring cup, hot plate stirrer, magnetic stirrer,
spatula, watch glass, mortal and pestle, analytical balance.
Furnace, oven (Binder, Germani), scanning electron
microscopy (SEM-EDX, Philips XL30; Germany), Fourier
Transform Infrared Spectrophotometer (Shimadzu 8021),
universal pH indicator, X-Ray Diffraction (Shimadzu XRD
6000).
B. Material
The materials used in this research are TBT (Tetrabuthyl
Titanate) (Sigma-Aldrich), white acrylic paint, ethanol pro-
analyst, glacial acetic acid and aquades.
III. PROCEDURE
A. Synthesis of TiO2 nanosols
The manufacture of nano TiO2 particles was carried out
by the sol-gel method using TBT as precursors, aquades, p.a
ethanol and glacial acetic acid. Nano sol was obtained by
mixing Tetrabuthyl Titanate (TBT) and ethanol p.a and then
sterilizing it for 30 minutes at room temperature and a clear
yellow solution was obtained. The solution was then added
to a mixture of glacial acetic acid, distilled water and ethanol
p.a dropwise (± 1 drop / second) with strong stirring. The
mixture is then stirred for 1 hour and a clear yellow light sol
is produced. The solution is then left in ambient conditions
for 24 hours. After being simulated for 24 hours, the sol-gel
Tis dried at 110ºC to convert the sol-gel phase to powder and
is ground for 2 hours at 500ºC. The powder formed was
characterized by FTIR and XRD [4].
B. Chemical Characterization of TiO2 nanosols with FTIR
The dried TiO2 powder was taken several mg to be mixed
with a few mg of dry KBr to be made pellet then analyzed
using FTIR.
C. Characterization of TiO2 nanosols by X-ray diffraction
(XRD)
The dried TiO2 powder is taken several mg for testing
and analyzed using X-ray diffraction (XRD) at an angle of 2θ
10º-100º.
D. Mixing TiO2 with Acrylic Paint and Coating on Glass
Media
TiO2 powder that has been planted is then mixed with
acrylic paint with a composition (gram) TiO 2 / Cat 0.5: 9.5;
1: 9; 1.5: 8.5; and 2: 8. Each mixing result is added with 2
mL of distilled water. The paint is then stirred with a spatula
until evenly distributed and coated on glass that has been
washed with distilled water and ethanol. Coating of paint /
TiO2 on the glass is done by the smear method. Ti-O
E. Self-Cleaning Test with Contact Angle measurement
Paint with the addition of TiO2 coated glass is then
measured by contact angle by means of a test of water drops
on the glass surface. The drip results are then photographed
using a Canon Ixus 230HS camera. Images from this shoot
are then analyzed using the AutoCAD application to measure
the angle of contact between water and glass surface.
OH buckling vibrations 1638,21
from Ti-OH
Stretching –OH vibrations 3418,39
from Ti-OH and ethanol
C. Characterization of TiO2 nanosols by X-ray diffraction
(XRD)
The results of the peak angle XRD test that appeared
were matched with JCPDS and the anatase phase was
obtained. This was evidenced by the presence of typical
anatase peaks seen at an angle of 2θ = 25.0707º with an
intensity of 100% and at several other peaks corresponding
to JCPDS anatase with number 21- 1272. To calculate the
size of the TiO2 FHHM crystals in Figure 2 are included in
the following Scherrer equation :

IV. RESULTS AND DISCUSSION

D = crystal size
A. Synthesis of TiO2 nanosols λ = wavelength of X-ray beam
In the TiO2 nanosol synthesis process hydrolysis and β = FWHM (full width half maximum) /
condensation reactions occur. In the hydrolysis stage, the intensity in radians
reaction takes place quickly where there is a change of θ = large angle from peak with high intensity.
alkoxide groups with nucleophilic hydroxyl groups. At the Obtained size of the synthesized TiO2 crystal is 24.32 nm.
condensation stage it will produce the formation and growth
of TiO2.xH2O [5].
B. Characterization of TiO2 nanosols with FTIR
Chemical characteristics of TiO2 nanosols from the
analysis of the chemical functional groups of TiO2 nanosols
using FTIR spectrophotometer are shown in Figure 1.

Figure 2. Synthesis of XRD TiO2 data (XRD

Philips X-pert Powder Diffractometer)
D. Self-Cleaning Test Results with Contact Angle
measurements
The ability of self-cleaning paint with the addition of
Figure 1. FTIR spectra of TiO2 synthesized by TiO2 TiO2 can be measured by how high the hydrophobic value of
the paint produced when coating a media. Paint / TiO 2
Based on the results obtained from the FTIR test in coated glass media are measured at the contact angle and the
Figure 1 shows the peaks that appear on several waves. The data produced in the Table 2 are:
FTIR spectrum on TiO2 shows the peak at wave number Table 2. Data of contact angle test result
3418.39 cm-1 which is the absorption of the stretching -OH Sample Drop Test Results Contact Angle
vibration, while the absorption of 1638.21 cm-1 which is the
Cat tanpa 62,6º
absorption of the bend -OH vibration. Based on the research
that has been carried out the bend -OH vibration of the Ti- TiO2
OH bond at the peak of 1650 cm -1 resulted from H2O
molecular adsorbent that is not completely released after
synthesis by the sol-gel method, whereas, at the peak of 3250 Cat + TiO2 67,6º
cm-1 is stretching vibration absorption -OH group of Ti-OH. 0,25 gr
The next spectrum appears at the peak of 467.50 cm -1
indicating the presence of Ti-O bonds.
Cat + TiO2 61,0º
Table 1. Functional group data on TiO2 nanosols 0,50 gr
Functional group Wave Number

Vibratory Ti-O from TiO2 467,50

 Cat + TiO2 86,1º
1,00 gr
Cat + TiO2 72,3º
1,50 gr
Cat + TiO2 102,2º
2,00 gr
The results of the test drops on paint without TiO 2
showed that the glass has a small contact angle because
when the water drops the paint is not round and the angle is
62.6 °. The 62.6 ° angle shows that this glass is not
hydrophobic because there are still many interactions of
water with the glass surface. The condition for an object to
be called hydrophobic is if it forms an angle of ˃90 °,
whereas for an object having a contact angle <90 ° then the
object is hydrophilic [6]
The results of the test drops on the glass coated with
paint/TiO2 with several variations of the mixture showed
that the glass coated with paint/TiO2 with several variations
of the mixture produced contact angles with a greater value
compared to the contact angle values produced by the paint
alone although the results were not significant. Paint / TiO 2
coated glass (9.25: 0.25), (9.5: 0.5), (9: 1), (8.5: 1.5), and (8:
2), produce a value The contact angles were 67.6°, 61.0°,
86.1°, 72.2° and 102.2° respectively. The contact angle
value in the paint / TiO2 composition has exceeded 90° so
that the resulting paint is already hydrophobic.
The hydrophobic nature of the paint increases with
increasing mass of TiO2 added. This happens because the
more TiO2 is added to the paint, the more nano TiO 2 coats
the surface so that nano-sized TiO2 will hold water from
dripping so it won't wet the surface. This is based on the
lotus effect on taro leaves. Taro leaves have a nano-sized
layer, this layer makes taro leaves and lotus leaves not wet.
The same principle is applied to surfaces coated with TiO 2
with nano size [7].
E. Morphological analysis of paint using Scanning
Electron Microscopy (SEM)
Analysis using SEM was conducted to determine the
surface morphology that formed on the surface of the paint.
Figure 3. Paint surface morphology with the addition of
TiO2 at 10,000 times magnification
The surface of the paint with the addition of TiO 2 is still
a lump which indicates that the mixing of the paint and TiO 2
is still not evenly distributed perfectly, causing a difference
in the contact angle values when the paint is tested for
hydrophobic properties between one surface and another.
SEM-EDX analysis of paint with the addition of TiO2.
Figure 4. Analysis of EDX paint with the addition of
TiO2
Figure 4 shows that TiO2 is found in paint. In paint with
the addition of TiO2 shows that there is TiO 2 in the paint.
This shows that the process of adding TiO 2 to the paint was
successful because of the TiO 2 that was embedded in the
paint even though the results were less than maximal at only
3.4%.
CONCLUSIONS AND SUGGESTIONS
Conclusion
Based on the results of research and discussion it can be
concluded that the XRD analysis of TiO2 synthesis results
has a crystal size of 24.32 nm. FTIR test shows the existence
of Ti-O group at wave number 467.5. The hydrophobic
nature test shows that the more TiO2 is added to the paint, the
better the hydrophobic properties.
Suggestion
It is recommended to vary the mixing of paint with more
TiO2 so that the best results can be known.
REFERENCES
[1] Mukti, K. H., Hastiawan, I., Rakhmawati, D., & Noviyanti, A. R.
2013. Preparasi Fotokatalis Barium Bismut Titanat
Terprotonasi(Hbbt) Untuk Fotodegradasi Metilen Biru. Prosiding
Seminar Nasional Sains dan Teknologi Nuklir PTNBR – BATAN
Bandung.
[2] Sutrisno, Hari. 2009. Tinjauan Mikrostruktur Kereaktifan Anatas Dan
Rutil Sebagai Material Superfotohidrofil Permukaan. Prosiding
Seminar Nasional Penelitian, Pendidikan dan Penerapan MIPA,
Fakultas MIPA, Universitas Negeri Yogyakarta.
[3] Maharani, D. K., Kartini, I., Aprilita, N. H. 2010. Nanosilica-Chitosan
Composite Coating on Cotton Fabrics. AIP Conference Proceedings
1284, 87.
[4] Tian, J., Chen, L., Yin, Y., Wang, X., Dai, J., Zhu, Z., Liu, X., & Wu,
P. 2009. Photocatalyst of TiO2/ZnO Nano Composite Film:
Preparation, Characterization, and Photodegradation Activity Of
Methyl Orange. Surface and Coating Technology, Vol. 204 No. 1,
205-214..
[5] Haryati, T. dan Mulyono T. 2013. Sintesis dan karakterisasi Core-
Shell ZnO/TiO2 sebagai Material Fotoanoda Dye Sensitized Solar
Cell (DSSC).
[6] Pravita S, Anggi, dan Dahlan, Dahyunir. 2013 . Sintesis Lapisan TiO2
Menggunakan Prekursor TiCl4 untuk Aplikasi Kaca Self Cleaning
dan Anti Fogging . Jurnal Fisika Unand Vol. 2, No. 2, ISSN 2302-
8491.
[7] Putri, T.A., Ratnawulan., & Ramli. 2018. Sintesis Lapisan
Hydrophobic Nanokomposit Mangan Oksida/Polystyrene (MnO2/PS)
untuk Aplikasi Self-Cleaning. Pillar of Physic. Vol. 11., No. 2. Hal: 1-
8.